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Accurate ab initio intermolecular potential energy surface for the quintet state of the O2(3Sigma<sub>g</sub><sup>-</sup>)–O2(3Sigma<sub>g</sub><sup>-</sup>) dimer
A new potential energy surface (PES) for the quintet state of rigid O2(3g-" align="middle"/>)+O2(3g-" align="middle"/>) has been obtained using restricted coupled-cluster theory with singles, doubles,...
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Towards universal potentials for (H2)2 and isotopic variants: Post-Born–Oppenheimer contributions
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Anharmonic vibrational frequencies and vibrationally averaged structures and nuclear magnetic resonance parameters of FHF−

J. Chem. Phys. 128, 214305 (2008); doi:10.1063/1.2933284

Published 3 June 2008

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So Hirata,1 Kiyoshi Yagi,2 S. Ajith Perera,1 Shiori Yamazaki,1 and Kimihiko Hirao2
1Quantum Theory Project, Department of Chemistry and Department of Physics, University of Florida, Gainesville, Florida 32611-8435, USA
2Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan and CREST, Japan Science and Technology Agency, Saitama 332-0012, Japan
The anharmonic vibrational frequencies of FHF− were computed by the vibrational self-consistent-field, configuration-interaction, and second-order perturbation methods with a multiresolution composite potential energy surface generated by the electronic coupled-cluster method with various basis sets. Anharmonic vibrational averaging was performed for the bond length and nuclear magnetic resonance indirect spin-spin coupling constants, where the latter computed by the equation-of-motion coupled-cluster method. The calculations placed the vibrational frequencies at 580 (nu1), 1292 (nu2), 1313 (nu3), 1837 (nu1+nu3), and 1864  cm−1 (nu1+nu2), the zero-point H–F bond length (r0) at 1.1539  Å, the zero-point one-bond spin-spin coupling constant [1J0(HF)] at 124  Hz, and the bond dissociation energy (D0) at 43.3  kcal/mol. They agreed excellently with the corresponding experimental values: nu1=583  cm−1, nu2=1286  cm−1, nu3=1331  cm−1, nu1+nu3=1849  cm−1, nu1+nu2=1858  cm−1, r0=1.1522  Å, 1J0(HF)=124±3  Hz, and D0=44.4±1.6  kcal/mol. The vibrationally averaged bond lengths matched closely the experimental values of five excited vibrational states, furnishing a highly dependable basis for correct band assignments. An adiabatic separation of high- (nu3) and low-frequency (nu1) stretching modes was examined and found to explain semiquantitatively the appearance of a nu1 progression on nu3. Our calculations predicted a value of 186  Hz for experimentally inaccessible 2J0(FF). ©2008 American Institute of Physics
History: Received 29 February 2008; accepted 30 April 2008; published 3 June 2008
Permalink: http://link.aip.org/link/?JCPSA6/128/214305/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.15.Mt
    Molecular rotation, vibration, and vibration-rotation constants
  • 31.15.xr
    Self-consistent-field methods in atomic and molecular physics
  • 31.15.bw
    Coupled-cluster theory
  • 31.15.vn
    Electron correlation calculations for diatomic molecules
  • 31.50.Df
    Potential energy surfaces for excited electronic states (atoms and molecules)
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • YEAR: 2008

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0021-9606 (print)   1089-7690 (online)
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